arXiv subjects

Viatcheslav Freger

Publications and source records attributed to Viatcheslav Freger.

5 recordsLinked to original sources

arXiv2026

Ion-Pairing Enhancement under Osmotic Stress: Disentangling the Effects of Ion and Water Activities

The dependence of ion pairing on osmotic stress may strongly affect the performance of ionic materials and membranes whose interior is often osmotically stresses, yet quantitative understanding of this dependence and, specifically, the effects of water and ion activities is limited. Motivated by this gap, we analyze the enhancement of ion pairing with osmotic pressure for concentrated aqueous KCl, NaCl, and LiCl solutions using molecular dynamics simulations. Based on rigorous thermodynamic relations, we separate the contributions of ion non-ideality to the pairing constant, varying with osmotic pressure, from other effects including water release and type of ion-pair. Our analysis reveals that ion non-ideality indirectly generates a stronger effect on pairing than the direct one of water release. However, its effect is moderated and may even be reversed for more hydrated pairs by a similarly large and opposite effect of ion-pair non-ideality assigned to varying dielectric properties of the solution and water restructuring upon pairing. The interplay between these contributions, including large and pair type-specific hydration effects on the cost of pairing, explains the observed opposing trends: pairing decreases with osmotic pressure for more hydrated solvent-separated pair types while increasing for contact pairs. The trend becomes more pronounced for more hydrated smaller cations, but was fairly independent of the water model used. The results further suggest that dielectric effects enhanced in ionic materials-and, as a result, larger variations of ion-pair non-ideality, compared with aqueous solutions, should have a more significant impact on pairing than water release.

cond-mat.soft↗

arXiv2026

Ion Permeation in Nanoscale Films: Fundamental Limitation and Evaluation of Dielectric Properties

Nanoscale films play a central role in biology and osmotic separations. Their water/salt selectivity is often regarded as intrinsic property, favoring thinner membranes for faster permeation. Here we highlight and quantify a fundamental limitation arising from the dependence of ion self-energy on film thickness, governed by its ratio to Bjerrum length. The resulting relation factors out this dependence from intrinsic ion permeability, which agrees well with available data and enables evaluation of dielectric properties of ultrathin films, advancing understanding of ion transport in membranes.

cond-mat.soft↗

arXiv2025

Isotopic Fingerprints of Proton-mediated Dielectric Relaxation in Solid and Liquid Water

We report cross-validated measurements of the isotope effect on dielectric relaxation for four isotopologues of ice and water, including the 1-10^5 Hz region, in which only sporadic and inconsistent measurements were previously available. In ice, the relaxation rates exhibit an activated temperature dependence with an isotope-independent activation energy. Across 248-273 K, the H_2O/D_2O relaxation rate ratio remains constant at 2.0 \pm 0.1. This scaling agrees with Kramers' theory in the high-friction limit if the moving mass is the proton or deuteron, indicating that dielectric relaxation is governed by a classic proton transfer over an energy barrier rather than molecular reorientation.

physics.chem-ph↗

arXiv2021

Simplifying concentration-polarization of trace-ions in pressure-driven membrane processes

Accounting for concentration-polarization (CP) is critical for modeling solute transport in membrane separation processes. In a mixed-electrolyte solution, ions CP is affected not only by diffusion and advection but also by electromigration. Yet, the classic film model, lacking an electromigration term, is frequently used for modeling ion CP. Often, ion CP is altogether neglected to reduce the computational load. Here, we study the CP of trace ions in a dominant salt solution, a case relevant for many reverse-osmosis and nanofiltration processes. First, we revisit the solution-diffusion-electromigration-film theory to obtain an analytical solution for the CP and membrane-transport of trace-ions in a dominant salt solution. Secondly, we consider limiting conditions relevant to reverse-osmosis and nanofiltration, from which we derive two compact equations that emerge as a seamless extension to the classic film theory. These equations can be used to account for the effect of electromigration on CP with minimal effort. Thirdly, we use our theory to quantify the effect of electromigration on ion CP in different dominant salt solutions. Finally, by analyzing two environmental membrane processes, we demonstrate how our theory deviates from the conventional one and quantify the implications on membrane scaling potential and the transport of ionic contaminants.

cond-mat.soft↗

arXiv2020

Water and Ion Transfer to Narrow Carbon Nanotubes: Roles of Exterior and Interior

Narrow carbon nanotubes (CNTs) desalinate water, mimicking water channels of biological membranes, yet the physics behind selectivity, especially, the effect of the membrane embedding CNTs on water and ion transfer, is still unclear. Here, we report $ab$ $initio$ analysis of the energies involved in transfer of water and K$^+$ and Cl$^-$ ions from solution to empty and water-filled 0.68 nm CNTs, for different dielectric constants $ε$ of the surrounding matrix. The transfer energies computed for $1 \leq ε< \infty$ permit a transparent breakdown of the transfer energy to three main contributions: binding to CNT, intra-CNT hydration, and dielectric polarization of the matrix. The latter scales inversely with $ε$ and is of the order $10^2$/$ε$ kJ/mol for both ions, which may change ion transfer from favorable to unfavorable, depending on ion, $ε$, and CNT diameter. This may have broad implications for designing and tuning selectivity of nanochannel-based devices.

cond-mat.mtrl-sci↗